Bis(methoxycarbonyl)sulfur diimide, a convenient reagent for the allylic amination of alkenes

The Synthesis of Ketone‐Derived Enamides by Elimination of HCN from Cyanoamides

“…[36] Indeed, heating 52 overnight at 60°C under the reaction conditions resulted in full conversion of initially formed 54 to the more stable Zaitzev isomer 53 E+Z in high yield. The reactions at room temperature were not regioselective.…”

“…It was considered possible that the initially formed Hofmann elimination product (54 and 57) isomerized partly to more stable isomers (53 E+Z and 54 E+Z). [36] Indeed, heating 52 overnight at 60°C under the reaction conditions resulted in full conversion of initially formed 54 to the more stable Zaitzev isomer 53 E+Z in high yield. These isomers (53E and 53Z) were separately con- firmed to be stable on heating under the reaction conditions.…”

“…This particular behavior of benzyl compounds 52 and 55 is compatible with the mechanism shown in Scheme 6. Compound 67 can be transiently deprotonated with NaOtBu to form conjugated dianion 68, [36] which on reprotonation, can lead to 67, 69E or 69Z. The charge in both 69E and 69Z is conjugated from the phenyl ring through to the carbonyl oxygen; deprotonation leading to 68 would interrupt this conjugation, and consequently, is not observed.…”

Chemo- and diastereoselective cyclopropanation of allylic amines and carbamates

“…Following General procedure 4, 46 (980 mg, 10.0 mmol), Bi (OTf) 3 (328 mg, 0.50 mmol), KPF 6 (92 mg, 0.50 mmol), methyl carbamate (1.13 g, 15.0 mmol) and MgSO 4 (w1.5 g) in THF (50 mL) were reacted for 16 h to give, after purification by flash column chromatography (eluent 30e40 C petrol/EtOAc, 1:0 to 9:1 gradient elution), 59 as a white solid (1.21 g, 78%);72 mp 25e26 C; d H (400 MHz, CDCl 3 ) 1.47e1.55 (1H, m, CH 2 ), 1.56e1.66 (2H, m, CH 2 ), 1.84e1.92 (1H, m, CH 2 ), 1.94e2.00 (2H, m, CH 2 ), 3.64 (3H, s, OMe)…”

Preparation and characterization of methyl 11‐amino‐(N‐p‐toluenesulfonyl)‐9‐E‐octadecenoate and methyl 8‐amino‐(N‐p‐toluenesulfonyl)‐9‐E‐octadecenoate

“…Extensive work has been done in the area of allylic halogenation and oxidation of fats and oils (1)(2)(3), but formation of allylic amines has received limited attention. It was reported that bis(N-p-toluenesulfonyl) sulfodiimide (1) may react with alkenes to form N-(allylic alkenyl) sulfinamidines (4,5). Allylic amination has been investigated (6-10), but these reactions have not been applied to fats and oils.…”